EP1338207A1 - Manufacturing process of tea beverages - Google Patents
Manufacturing process of tea beverages Download PDFInfo
- Publication number
- EP1338207A1 EP1338207A1 EP03003706A EP03003706A EP1338207A1 EP 1338207 A1 EP1338207 A1 EP 1338207A1 EP 03003706 A EP03003706 A EP 03003706A EP 03003706 A EP03003706 A EP 03003706A EP 1338207 A1 EP1338207 A1 EP 1338207A1
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- European Patent Office
- Prior art keywords
- tea
- formulation
- strictinin
- extract
- sterilization
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23F—COFFEE; TEA; THEIR SUBSTITUTES; MANUFACTURE, PREPARATION, OR INFUSION THEREOF
- A23F3/00—Tea; Tea substitutes; Preparations thereof
- A23F3/16—Tea extraction; Tea extracts; Treating tea extract; Making instant tea
- A23F3/163—Liquid or semi-liquid tea extract preparations, e.g. gels, liquid extracts in solid capsules
-
- A—HUMAN NECESSITIES
- A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
- A23F—COFFEE; TEA; THEIR SUBSTITUTES; MANUFACTURE, PREPARATION, OR INFUSION THEREOF
- A23F3/00—Tea; Tea substitutes; Preparations thereof
- A23F3/16—Tea extraction; Tea extracts; Treating tea extract; Making instant tea
- A23F3/18—Extraction of water soluble tea constituents
Definitions
- the present invention relates to a process for manufacturing tea beverages, suitable for the tea beverages filled in containers that sediments do not occur even during the long-term storage. It particularly relates to a process that can prevent from the occurrence of secondary sediment predicting the occurrence of the secondary sediment.
- green tea beverages tightly filled in cans or plastic bottles have been continuously developed.
- green tea beverages have something flocky, floating, or white turbidly suspended matter, or precipitate, that is, "sediment” occurs, and this is a problem for the beverages.
- sediment occurs, especially, in the case of green tea beverages filled in clear bottles, the marketability will be lost due to the visual impressions.
- the said sediment can be classified into “primary sediment” and "secondary sediment,” where the primary sediment occurs immediately after the production of tea beverages, while the secondary sediment occurs gradually with time during the storage of the products.
- the primary sediment obviously occurs where caffeine bind with tannin or protein. It has been confirmed, as a preventing method, that the occurrence of the primary sediment can be surely prevented by kieselguhr filtration or membrane filtration after centrifugal separation of a tea extract.
- the extract contains a high concentration of flavonol in the un-oxidized state at first.
- the flavonol particularly, a catechin component
- metal ions such as calcium, magnesium, aluminum, zinc or iron
- oxidized polyphenol gradually binds with caffeine, proteins, pectin or polysaccharides by the catalytic action of metal ions to form complexes.
- green tea beverage turns the color from clear light green to brown, the suspended matter gradually begins to occur, and then, the visible flock secondary sediment is formed.”
- the conventional manufacturing processes of tea beverages to prevent the occurrence of secondary sediment are mainly the following 4 methods:
- Japanese unexamined patent publication No. 63-036745 discloses a treatment of a tea extract by adjusting a tea extract at 5-15°C with an ultrafiltration membrane (molecular weight of 10,000-100,000), and removing the tea cream.
- Japanese unexamined patent publication No. 04-045744 discloses a manufacturing process of clear green tea beverages by fractionating water-soluble tea components obtained by extracting green tea leaves, fresh or dry tea leaves by ultrafiltration, and removing macromolecular components having a molecular weight of 10,000 or more.
- Japanese examined patent publication No. 07-097965 discloses a method to clarify beverages by adding ascorbic acid to a green tea extract to acidify, cooling rapidly, centrifuging, and then, filtrating with kieselguhr.
- Japanese unexamined patent publication No. 06-269246 discloses a method to clarify beverages by extracting a green tea with warm water, cooling the obtained extract, adding tannic acid to the extract, standing still, removing fine tea particulates by centrifuging, and then, filtrating with kieselguhr.
- 11-056241 discloses a manufacturing process of tea beverages by adding sodium ascorbate to a extract obtained by extracting tea leaves, followed by cross-flow system with microfiltration membranes.
- Japanese unexamined patent publication No. 06-311847 discloses a method for preventing from the precipitation of the sediment by adding chitosan to a water-soluble component of green tea, adsorbing macromolecular polyphenol, adsorbing and recovering the adsorbed chitosan and the residual chitosan with kieselguhr.
- Japanese unexamined patent publication No. 08-228684 discloses a method to effectively inhibit the occurrence of secondary sediment of green tea beverages, by centrifuging or cloth-filtering the warm-water extract of green tea, further combining with a process adding an enzyme having a hemi-cellulose activity.
- Japanese unexamined patent publication No.2001-045973 discloses a method to inhibit the occurrence of flock in beverages, by adding ⁇ -amylase to a green tea extract.
- U.S. Patent No. 4,501,261 can be referred to as the method c).
- Japanese Patent No. 3,152,416 discloses a method for producing tea, by treating with a cation exchange resin having a sulfonic acid group previously bonded with potassium ion.
- the present invention is a manufacturing process for preparing a tea beverage comprising the following steps: an extraction process extracting raw tea leaves, a filtration process filtrating the extract, a formulation process adjusting the concentration of extract and pH, and a sterilization process sterilizing the formulation, characterized in having a process determining the strictinin content in a tea extract or formulation, characterized in that the manufacturing process of tea beverages carrying out with a process determining the strictinin content in a tea extract or formulation during the process.
- the strictinin is a compound (1-O-galloyl-4,6-O-(S)-hexahydroxydiphenoyl - ⁇ -D-glucose) shown by the following chemical formula 1, and is one of tannins, particularly, ellagitannins extracted from tea.
- ellagitannins extracted from tea.
- FIG. 1 is a schematic chart of a working procedure of Test 2;
- FIG. 2 is a graph showing the results of the determination by high performance liquid chromatography (HPLC) of strictinin contents and ellagic acid contents of both "prepared solution of before-heat-sterilization" and "prepared solution of after-heat-sterilization” after the purified strictinin solution is retort-sterilized in Test 4;
- HPLC high performance liquid chromatography
- FIG. 3 is a graph showing the results of the determination by HPLC of strictinin contents and ellagic acid contents of both the "prepared solution of before-heat-sterilization" and the "prepared solution of after-heat-sterilization” after the prepared solution, obtained by adding the purified strictinin to the "HP-20 unadsorbed-fraction" obtained in Test 1, is retort-sterilized in Test 4;
- FIG. 4 is a graph as determined in Test 11 that the occurrence or non-occurrence of the secondary sediment is plotted on the coordinate, the abscissa axis indicates the strictinin concentration (weight %) in the tea leaves by the hot-water extraction, and the ordinate axis indicates the strictinin concentration (ppm) in the formulation in the case that the Brix is adjusted to 0.3 (0.23 by weigh of tea solid).
- FIG. 5 is a graph as determined in Test 11 that the occurrence or non-occurrence of the secondary sediment is plotted on the coordinate, the abscissa axis indicates the strictinin concentration (weight %) in the tea leaves by the acidic extraction, and the ordinate axis indicates the strictinin concentration (ppm) in the formulation in the case that the Brix is adjusted to 0.3 (0.23 by weigh of tea solid).
- FIG. 6 is a graph as determined in Test 12 that the occurrence or non-occurrence of the secondary sediment is plotted on the coordinate, the abscissa axis indicates the strictinin concentration (weight %) in the tea leaves by the hot-water extraction, and the ordinate axis indicates the strictinin concentration (ppm) in formulation in the case that the Brix is adjusted to 0.3 (0.23 by weigh of tea solid).
- FIG. 7 is a graph as determined in Test 12 that the occurrence or non-occurrence of the secondary sediment is plotted on the coordinate, the abscissa axis indicates the strictinin concentration (weight %) in the tea leaves by the acidic extraction, and the ordinate axis indicates the strictinin concentration (ppm) in the formulation in the case that the Brix is adjusted to 0.3 (0.23 by weigh of tea solid).
- the present invention provides a process for manufacturing tea beverages, including a process determining the strictinin content in a tea extract or formulation.
- One of the examples for the manufacturing process of tea beverages is: determining the strictinin content of a tea extract or formulation, and specifying the strictinin content as an indicator to design a manufacturing process (planning) or to manage manufacturing conditions.
- the strictinin content as an indicator in the case of light-fermented tea, it is preferable to determine the strictinin content in a tea extract or formulation about 14 ppm or less, more desirably, about 13 ppm or less, or to determine the strictinin content in the tea solid portion of the tea extract or formulation about 0.5-1.1% or less, more preferably, about 0.6-0.8% or less.
- the strictinin content in a tea extract or formulation is preferable to determine the strictinin content in a tea extract or formulation about 6 ppm or less, more preferably, about 5 ppm or less, or to determine the strictinin content in the tea solid portion of the tea extract or formulation about 0.2-0.5% or less, more preferably, about 0.2-0.4% or less.
- the tea solid portion of a tea extract or formulation is the solid components (except for water) derived from tea, such as tannin, catechin and strictinin contained in leaves or stems of plant tea (Camellia sinensis), but excluding the solid portion formed when ascorbic acid or sodium bicarbonate is added during the manufacturing process.
- the amount of tea solid portion is the amount of tea solid components.
- the manufacturing process of tea beverages in the present invention provides clear tea beverages without the secondary sediment occurrence even if they are stored for a long-term period.
- the present invention provides the tea beverages suitable for filling in containers, such as cans, plastic bottles (including polyethylene terephthalate (PET) bottles), glass bottles and paper containers.
- containers such as cans, plastic bottles (including polyethylene terephthalate (PET) bottles), glass bottles and paper containers.
- the occurrence of the secondary sediment during the storage of tea beverages can be exactly predicted by only determining the strictinin content in a tea extract or formulation of before-heat-sterilization. Further, designing the manufacturing process or managing the conditions only with the strictinin content in the tea extract or formulation as an indicator can prevent the occurrence of the secondary sediment. For example, when the raw tea leaves having a low strictinin content is used, where the strictinin content in the tea extract or formulation of before-heat-sterilization is at or below the predetermined level, it is unnecessary to control and treat for the prevention of the secondary sediment occurrence in all the processes, such as extraction, filtration and formulation, of a production line.
- the raw tea leaves having relatively high strictinin content is used, it is only necessary to design and determine the conditions of all the processes just with the strictinin content as an indicator in the tea extract or formulation. Therefore, the indicators in the manufacturing management are simple and clear, resulting in the reduced labor significantly in the manufacturing management to prevent the occurrence of the secondary sediment in the present invention as compared with the conventional processes.
- the conventional manufacturing processes of tea beverages preventing the occurrence of secondary sediment, especially, many of those removing the cause substances of the secondary sediment from a tea extract or formulation are the methods removing the substances binding with ellagic acid formed by the decomposition of strictinin.
- Such substances like protein, contain substances affect the flavor and pharmacological components in tea beverages, so the originally contained flavor and pharmacological components in a tea must have been lost.
- the originally contained flavor and pharmacological components in tea leaves can be maintained in tea beverages by only reducing the strictinin content, since the substances, such as protein, binding with ellagic acid can be remained much more in tea beverages.
- Tea in the present invention is the tea as a raw material, including leaves and stems, used for manufacturing tea beverages, and also, including any of fresh, crude and refined tea leaves.
- “Secondary sediment” in the present invention is a flock (flocculent) suspended matter or sediment, but excluding fine powder sediment, and it should be distinguished from the "primary sediment”.
- the manufacturing process of tea beverages in the present invention can be carried out during the conventional process, either by adjusting the strictinin content of a tea extract or formulation, before treating it with heat-sterilization, of about 6 ppm or less, more preferably, about 5 ppm or less; or by adjusting the strictinin content of the tea solid portion of the tea extract or formulation of before-heat-sterilization about 0.2-0.5% or less, more preferably, about 0.2-0.4% or less.
- the process can be also carried out with the ratio, as an indicator, of the tannin or amino acid content and the strictinin content in a tea extract and formulation.
- the above-mentioned conventional process in this case is, for example, a manufacturing process of green tea beverages having a series of: an extraction process extracting raw tea leaves, a filtration process filtrating the extract, a formulation process adjusting the concentration of the extract and the pH, and a sterilization process sterilizing the formulation.
- the manufacturing process of tea beverages in the present invention is not necessarily restricted to the above-embodiment only.
- the strictinin content in a tea extract or formulation of before-heat-sterilization it is preferable to determine the strictinin content in a tea extract or formulation of before-heat-sterilization, and in order to adjust the strictinin content at or below the above-mentioned predetermined level, design the manufacturing process on: selecting raw tea leaves; specifying the process of the raw tea leaves; specifying the conditions of extraction, filtration or formulation; specifying the formulation materials and their formulating ratios; and specifying the process of the tea extract or formulation.
- the production line starts operating, it is required to determine and adjust the strictinin content in the tea extract or formulation before-heat-sterilization to keep the strictinin content at or below the predetermined level by controlling the manufacturing process.
- the design and management of the process in the present invention is not restricted only to the above embodiment.
- the determination of the strictinin content in the tea extract or formulation is possibly carried out at any time before heat-sterilization, but more preferably, carried out at just before the heat-sterilization.
- any kind of tea is applicable if the leaves or stems are plucked from the tea plant, Camellia sinensis (botanic name), and as long as they are Camellia sinensis, it is not also a matter of question as for their varieties, products area, plucking period and means, and cultivating methods.
- Fresh tea, including leaves and stems, is also applicable as a raw material.
- any kind of non-fermented tea with the crude tea process stopping the ferment activity by steaming or roasting the fresh tea leaves is applicable as the raw tea leaves, such as Sen-cha, Kamairi-cha, Kabuse-cha, Gyokuro, Ten-cha, Matcha, Ban-cha, Houji-cha, Steamed tamaryoku-cha and Pan-fired tamaryoku-cha.
- the non-fermented tea more than two of them may be mixed together, and flavors may be added to them.
- a light-fermented tea such as Jasmine tea, is applicable as a raw material.
- the semi-fermented tea like Oolong tea
- the fermented tea like Black tea
- the post-heating fermented tea like Pu-erh tea
- the cream-down appearing in, for example, Oolong tea and black tea is derived from other causes, which differ from the irreversible flock secondary sediment in the non-fermented tea of, for example, green tea.
- the inventors found that the differences in the varieties, products area, plucking time and means, and cultivating methods of raw tea leaves result in the differences in the strictinin contents in tea leaves, as well. Therefore, when the strictinin content in a tea extract or formulation before the process of heat-sterilization exceeds the predetermined level, the strictinin content of the said tea extract or formulation can be adjusted below the predetermined level by selecting the raw tea leaves having a low strictinin content.
- the strictinin contents in different kinds of tea leaves in order to select the tea leaves having the lower strictinin content among them.
- the strictinin content in the extract or formulation is about 6 ppm or less.
- the strictinin content of the extract or formulation is the level that the secondary sediment does not occur in any condition during the manufacturing process.
- the above-mentioned raw tea leaves if necessary, is treated by the well-known finishing-process, and the obtained finished tea is subjected to the next extraction process. There, the finishing process does not affect the strictinin content in the tea extract.
- extraction of raw tea leaves can be done, as is well known, in the ordinary process using an extractor called “kneader”, extracting with 20-50 times of extraction water to the raw tea leaves at 0-100°C under an atmospheric pressure for about 1-20 minutes, stirring the extract one to several times, if necessary.
- the extraction methods and conditions are not necessarily restricted to the above, and the extraction at an applied pressure is also applicable.
- the extraction water used at the extraction hard water, soft water, ion-exchanged water, natural water, aqueous solution containing ascorbic acid or pH-adjusted water are applicable. Since the strictinin content of the extract obtained by extraction is affected by pH of the extraction water, the strictinin content of the extract increases when the pH of the extraction water is adjusted at an acidic range, especially, pH4.5 or less. On the other hand, the strictinin content of the extract can be reduced by increasing the pH of the extract, for example, by adjusting the pH at a weak or neutral acidic range.
- the strictininin content of a tea formulation of before-heat-sterilization exceeds the predetermined level
- the extracted amount of strictinin can be effectively controlled by adjusting the extraction water to pH5 or above, more preferably, to pH6 or above.
- such extraction in a weak or neutral acidic range is disclosed as just one of the techniques reducing the strictinin concentration in the extract, so that it is not necessarily preferable to carry out the extraction at a weak or neutral acidic range for the manufacturing process in the present invention. This is because, as the pH increases, the deterioration of catechin is facilitated. There, it is preferable to adjust the extract to pH 6.5-7 at most.
- the extracting temperature namely, the temperature of the warm extraction water
- warm water of 45-100°C, more preferably, 60-90°C.
- the extract obtained by extraction is subjected to cool about 5-40°C, if necessary.
- the extract is, if necessary, adjusted at an acidic range of pH4-5 by adding ascorbic acid and sodium ascorbate to the extract before, after, or at the same time of cooling the extract.
- By cooling or acidity adjusting of the extract it is possible to prevent the oxidation of the extracted components, as well as increasing the efficiency of the next centrifugation process by precipitating the cause substances of the primary sediment.
- the crude filtration removing the extraction residue such as tealeaves or large fine powder
- the filtration removing the cause substances of the primary sediment It is optional to carry out the said crude filtration or the said filtration removing the cause substances of the primary sediment anywhere in the manufacturing process.
- Removing the cause substances of primary sediment can be carried out by kieselguhr filtration or other appropriate membrane filtrations.
- Centrifugation may be carried out at 5,000-10,000 rpm, and it is preferable to cool the extract or formulation about 5-40°C prior to centrifugation.
- the membrane separations such as microfiltration, ultrafiltration, reverse osmosis membrane filtration, electro-dialysis and bio-functional membrane can be carried out, and the combination with the above-mentioned kieselguhr filtration using a filter aid is also applicable.
- the pH, concentrations (Brix value), and tastes are adjusted by adding at least one or more of water (hard water, soft water, ion-exchanged water, natural water and others), ascorbic acid, sodium ascorbate, sodium bicarbonate, saccharides, dextrin, flavor, emulsifier, stabilizer or other seasoning materials.
- the concentration (Brix value) decreases, the strictinin concentration as well as the concentration of the binding components, such as protein, bind with "ellagic acid" derived from the decomposition of the strictinin by heat-sterilization, also decreases, so that the occurrence of secondary sediment is prevented. Therefore, when the strictinin content of a tea formulation of before-heat-sterilization is determined and exceeds the predetermined level, decreasing the concentration (Brix value) of the tea formulation is one of the countermeasures in the manufacturing management. However, in order to keep a good flavor of the tea beverages, it is preferable to concentrate the tea formulation (Brix value) to 0.1-0.4, more preferably, to 0.2-0.3.
- the formulation for the "heat-sterilization process", after the re-heating (when it is necessary), filling the formulation to retort-sterilize at 121°C for 7 minutes under an appropriate pressure, such as at 1.2mmHg, for can beverages; or to carry out the ultra high temperature (UHT) sterilization keeping the formulation at 120-150°C for one second to several tens of seconds for plastic-bottle beverages.
- an appropriate pressure such as at 1.2mmHg
- the clear correlation between the selection on methods or conditions of heat-sterilization and the strictinin content has not been established yet, in the present invention, it is preferable to control the manufacturing process with a predetermined value as an indicator, where the contents of ellagic acid and strictinin in a tea formulation of after-heat-sterilization are determined by changing the methods or conditions of heat-sterilization in various ways.
- extraction water ion-exchanged water
- determining the strictinin contents of the tea extract or formulation of several kinds of raw tea leaves to examine whether the strictinin content exceeds a predetermined level selecting the raw tea leaves that the strictinin contents do not exceed the predetermined level from which, considering such as the flavor, specify the raw tea leaves.
- the present inventors found that when the varieties, products area, plucking period and means, and cultivating methods are different, the strictinin contents of the tea leaves are different.
- determining the content with high performance liquid chromatography is applicable.
- 200ml of the obtained "HP-20 unadsorbed-fraction" (Brix 0.4) is adjusted to 500ml, pH6.0 and the ascorbic acid concentration of 500 ppm with ascorbic acid, sodium bicarbonate and ion-exchanged water, to be heat-sterilized at 121°C for 7 minutes, stored at 37°C, and observed.
- 0.5g of the obtained "HP-20 adsorbed-80%-methanol-fraction" is adjusted to 500ml, pH6.0 and the ascorbic acid concentration of 500 ppm with ascorbic acid, sodium bicarbonate and ion-exchanged water, to be heat-sterilized at 121°C for 7 minutes, stored at 37°C, and observed.
- the sediment-forming test is carried out as in Test 1, by adding the each obtained fraction to the "HP-20 unadsorbed-fraction" (Brix 0.4).
- the formation of secondary sediment is observed in the "HP-20 adsorbed-20%-methanol-fraction” and the "HP-20 adsorbed-40%-methanol-fraction".
- the formation amount of the sediment, especially, in the "HP-20 adsorbed-20%-methanol-fraction" is rich.
- the sediment formation is observed in peak 3.
- the peak 3 is identified with Liquid Chromatography-Mass Spectrometer (LC-MS) and Nuclear Magnetic Resonance (NMR).
- the identified sediment is the strictinin.
- the retort-sterilized strictinin forms the ellagic acid.
- ellagic acid is rarely detected in the "prepared solution of after-heat-sterilization".
- the strictinin in the beverage decomposes to form ellagic acid, and said ellagic acid binds with a component contained in the "HP-20 unadsorbed-fraction" to form precipitates, that is, the secondary sediment.
- the supernatant liquid is filtrated with a microfiltration membrane (1 ⁇ m MF membrane, Advantec Toyo Kaisha, Ltd.) to add 0.5g ascorbic acid, to adjust the solution to 200ml with ion-exchange water to obtain a formulation.
- the strictinin concentration of the said formulation is determined by HPLC as in Test 3. The results are shown in Table 4.
- the above-mentioned acidic aqueous solution is prepared by adding 0.5g ascorbic acid to 800ml and pH5.9 ion-exchanged water to adjust to pH 3.4
- the basic aqueous solution is prepared by adding 0.5g sodium carbonate to 800ml ion-exchanged water to adjust to pH 8.5.
- the strictinin in the tea extract decomposed by heat-sterilization forms ellagic acid, and said ellagic acid binds with components contained in the "HP-20 unadsorbed-fraction" to form flock precipitates, that is, the secondary sediment in the tea beverages.
- the flock precipitates are found in the bovine serum albumin solution of after-heat-sterilization, but not in the solution of before-heat-sterilization.
- the substances bind with ellagic acid which form precipitates are amino acids, peptides and proteins, due to the deterioration of said components by heat-sterilization or long-term-storage.
- test solution is prepared according to the "Hot-water extraction method” adopted in the preparation method of the test solution in tannin assay of tea in the official analysis method ("Quantitative Analysis of Tea Constituents", Tea Research Journal No.71, p52 (1990), The Ministry of Agriculture, Forestry and Fisheries, National Research Institute of Vegetable, Ornamental Plants and Tea)
- another test solution is prepared according to the "Acidic hot-water extraction method" which is the originally developed process in the present invention modified from the hot-water extraction process.
- the ratio of strictinin solid portion in the tea solid portion in Table 9 is the strictinin content (%) to the whole tea solid portion in the formulation.
- Table 10 shows that the strictinin concentrations in the tea leaves by the hot-water extraction in Table 9 are arranged in descending order
- Table 11 shows that the strictinin concentrations in the tea leaves by the acidic extraction in Table 9 are arranged in descending order.
- FIG. 4 is a graph that the occurrence or non-occurrence of the secondary sediment is plotted on the coordinate, the abscissa axis indicates the strictinin concentration (weight %) in the tea leaves by the hot-water extraction, and the ordinate axis indicates the strictinin concentration (ppm) in the formulation in the case that the Brix is adjusted at 0.3 (0.23 by weigh of tea solid).
- FIG. 5 is a graph that the occurrence or non-occurrence of the secondary sediment is plotted on the coordinate, the abscissa axis indicates the strictinin concentration (weight %) in the tea leaves by the acidic extraction, and the ordinate axis indicates the strictinin concentration (ppm) in the formulation in the case that the Brix is adjusted at 0.3 (0.23 by weigh of tea solid).
- the extracted amount of strictinin is small by the hot-water extraction method adopted in the official method for the analysis of tannin, the extracted amount of strictinin is effectively increased by the acidic hot-water extraction method. Moreover, as clearly seen in FIGS. 4 and 5, the determination by the acidic hot-water extraction method has a greater correlation with the occurrence of the secondary sediment than that by the hot-water extraction method. From the result, it is preferable to adopt the acidic hot-water extraction method, preferably, the method carried out with the condition of pH2-4 at 70-100°C for the determination of the strictinin contents in raw tea leaves.
- the occurrence of the secondary sediment can be prevented when the strictinin content to the tea solid portion in a tea extract or formulation is controlled so as to be about 0.2-0.5 % or less, specifically, about 0.2-0.4 % or less.
- it is preferable to control the upper limit of the strictinin content of the tea solid portion depending on the tea solid concentration of the formulation as an indicator.
- the tea solid concentration (Brix) of tea extract or formulation is 0.23
- the strictinin content when the Brix is 0.18, the strictinin content to be 0.34%, and when the Brix is 0.13, the strictinin content to be 0.48% to the tea solid portion.
- ascorbic acid is added adjusting pH6.0, Brix 0.1-0.3 (0.03-0.23 in weigh of tea solid) and ascorbic acid of 500 ppm with ion-exchanged water and sodium bicarbonate to obtain formulations, in order to determine the strictinin concentrations in the formulations by HPLC as in Test 3.
- the ratio of strictinin solid portion in the tea solid portion in Table 12 is the strictinin content (%) to the whole tea solid in the formulation.
- Table 13 shows that the strictinin concentrations in the tea leaves by hot-water extraction in Table 12 are arranged in descending
- Table 14 shows that the strictinin concentrations in the tea leaves by acidic extraction in Table 12 are arranged in descending order.
- FIG. 6 is a graph that the occurrence or non-occurrence of the secondary sediment is plotted on the coordinate, the abscissa axis indicates the strictinin concentration (weight %) in the tea leaves by the hot-water extraction, and the ordinate axis indicates the strictinin concentration (ppm) in formulation in the case that Brix is adjusted at 0.3 (0.23 by weigh of tea solid).
- FIG. 7 is a graph that the occurrence or non-occurrence of the secondary sediment is plotted on the coordinate, the abscissa axis indicates the strictinin concentration (weight %) in the tea leaves by the acidic extraction, and the ordinate axis indicates the strictinin concentration (ppm) in the formulation in the case that Brix is adjusted at 0.3 (0.23 by weigh of tea solid).
- the extracted amount of strictinin in case of Jasmine tea is also small by the hot-water extraction method adopted in the official method for the analysis of tannin, the extracted amount of strictinin is effectively increased by the acidic hot-water extraction method.
- the determination by the acidic hot-water extraction method has a greater correlation with the occurrence of the secondary sediment than that by the hot-water extraction method. From the above, also in case of Jasmine tea, it is preferable to adopt the acidic hot-water extraction method about pH 4.5 or less, at about 60-100°C and for about 5-60 minutes, or more preferably, pH 2.0-4.0, 70-100°C and for 10-30 minutes for the determination of the strictinin content in the raw tea leaves.
- the occurrence of the secondary sediment can be prevented when the strictinin content to the tea solid portion in a tea extract or formulation is controlled so as to be about 0.5-1.1% or less, especially, about 0.6-0.8% or less.
- the tea solid concentration (Brix) of the tea extract or formulation is 0.23, it is preferable to specify the upper limits of the strictinin content to the tea solid portion as 0.62%.
- the strictinin content when the Brix is 0.18, the strictinin content to be 0.80%, and when the Brix is 0.13, the strictinin content to be 1.11% to the tea solid portion.
Abstract
Description
| | | | |
HP-20 unadsorbed-fraction | ||||
HP-20 adsorbed-80%-methanol-fraction | ||||
HP-20 unadsorbed-fraction + | ||||
HP-20 adsorbed-80%-methanol-fraction |
Apparatus | Hitachi D-7000 Advanced HPLC, D-7000 type of advanced |
HPLC system manager | |
Column | Wakosil-II 5 C 18HG 4.6 X (30+250) |
Column temperature | |
40°C | |
Flow rate | 0.6 ml/min |
Detection | UV280 |
Mobile phase A | 15% MeOH (containing 0.1% phosphoric acid) |
|
45% MeOH (containing 0.1% phosphoric acid) |
Time (min.) | Mobile phase A | Mobile Phase B |
0.0 min. | 100% | 0% |
20.0 min. | 100% | 0% |
20.1 mm. | 0% | 100% |
40.0 min. | 0% | 100% |
40.1 min. | 100% | 0% |
60.0 min. | 100% | 0% |
Amount of strictinin/ppm | |
Formulation of before-heat-sterilization | 15.3 |
Formulation of after-heat- | 0 |
pH of extractions | Brix of formulations | Strictinin in formulations |
8.5 pH | 0.404 % | 15.9 ppm |
5.9 pH | 0.400 % | 21.4 ppm |
3.4 pH | 0.400 % | 33.4 ppm |
Extraction temperatures | Brix of formulations | Strictinin in formulations |
90°C | 0.417% | 36.6 ppm |
70°C | 0.404% | 34.1 |
50°C | 0.351% | 25.0 |
30°C | 0.316 % | 15.0 ppm |
Extraction times | Brix of formulations | Strictinin in |
3 min. | 0.359 % | 23.2 |
5 min. | 0.396 % | 29.2 |
20 min. | 0.428 % | 34.7 ppm |
Sediment Occurrence after 3 days at 37°C | |
Ellagic acid only | |
Ellagic acid + HP-20 unadsorbed-fraction |
Standards | Administration (mg) | Standards | Administration (mg) |
Aspartic acid | 3.18 | Valine | 2.97 |
Serine | 2.51 | Methionine | 2.89 |
Glutamic acid | 2.05 | Lysine | 1.95 |
Glycine | 1.39 | Isoleucine | 2.62 |
Histidine | 1.96 | Leucine | 3.33 |
Arginine | 1.52 | Phenylalanine | 3.00 |
Threonine | 1.02 | Glutamine | 4.25 |
Alanine | 1.16 | Asparagin | 6.31 |
Proline | 0.94 | Theanine | 3.03 |
Cysteine | 2.20 | Bovine Serum Albumin | 2.47 |
Tyrosine | 3.61 |
Green Tea Lot Nos. | Strictinin in Crude Tea/Wt. % | Strictinin in Formulations ppm (*%) | Sediment Formation Stored at 37°C | ||||
Acidic Ext. | H-W Ext. | | | | | ||
| 0.439 | 0.173 | 11.48(0.51) | ++ | ++ | ++ | ++ |
| 0.436 | 0.158 | 11.18(0.49) | ++ | ++ | ++ | ++ |
| 0.390 | 0.101 | 6.50(0.29) | - | - | - | |
Lot | |||||||
4 | 0.369 | 0.126 | 6.00(0.27) | - | - | - | - |
| 0.370 | 0.120 | 5.80(0.26) | - | - | - | - |
| 0.399 | 0.110 | 6.88(0.30) | - | - | - | + |
Lot 7 | 0.362 | 0.094 | 5.80 (0.26) | - | - | - | - |
Lot 8 | 0.349 | 0.086 | 5.75 (0.25) | - | - | - | - |
Lot 9 | 0.410 | 0.126 | 7.13(0.32) | - | - | + | + |
| 0.426 | 0.125 | 8.09(0.36) | + | + | + | + |
Lot 11 | 0.430 | 0.140 | 8.59(0.38) | + | + | + | + |
Lot 12 | 0.308 | 0.052 | 3.70(0.16) | - | - | - | - |
Lot 13 | 0.286 | 0.050 | 2.90(0.13) | - | - | - | - |
Lot 14 | 0.322 | 0.072 | 4.60 (0.20) | - | - | - | - |
Ext.: Extraction (%): Ration of strictinin solid portion +: Sediment was formed
H-W Ext.: Hot-water Extraction in tea solid portion ++: Rich in sediment
Jasmine Tea Lot Nos. | Strictinin in Jasmine Tea/Wt. % | Strictinin in Formulations | Sediment Formation Stored at 37°C | ||||
Acidic Ext. | H-W Ext. | ppm (*%) | | | | | |
| 1.049 | 0.601 | 26.94 (1.19) | ++ | ++ | ++ | ++ |
| 0.907 | 0.494 | 21.52 (0.95) | + | ++ | ++ | ++ |
| 0.769 | 0.491 | 18.43 (0.82) | + | + | + | + |
| 0.578 | 0.365 | 13.81 (0.61) | - | - | - | - |
| 0.574 | 0.354 | 13.18 (0.58) | - | - | - | - |
| 0.585 | 0.333 | 13.81 (0.61) | - | - | - | - |
Lot 7 | 0.736 | 0.440 | 16.46 (0.73) | + | + | + | + |
Lot 8 | 0.667 | 0.336 | 14.86 (0.66) | - | - | - | + |
Lot 9 | 0.732 | 0.398 | 15.85 (0.70) | - | - | - | |
Lot | |||||||
10 | 0.613 | 0.333 | 14.63 (0.65) | - | - | + | + |
Lot 11 | 0.508 | 0.321 | 12.79 (0.57) | - | - | - | - |
Lot 12 | 0.444 | 0.241 | 10.30 (0.46) | - | - | - | - |
Lot 13 | 0.383 | 0.198 | 8.54 (0.38) | - | - | - | - |
Ext.: Extraction (%): Ration of strictinin solid portion +: Sediment was formed
H-W Ext.: Hot-water Extraction in tea solid portion ++: Rich in sediment
Claims (10)
- A manufacturing process for preparing a tea beverage comprising the following steps:an extraction process extracting raw tea leaves,a filtration process filtrating the extract,a formulation process adjusting the concentration of extract and pH, anda sterilization process sterilizing the formulation,
having a process determining the strictinin content in a tea extract or formulation. - A manufacturing process for preparing a tea beverage of claim 1,
characterized in
determining the strictinin content in a tea extract or formulation; and
specifying the strictinin content as an indicator, carrying out one or more of manufacturing management on selecting raw tea leaves, specifying the treatment conditions of before heat-sterilization-process, or formulating. - A manufacturing process for preparing a tea beverage of claim 1,
characterized in
determining the strictinin content in a tea extract or formulation before treating it with heat-sterilization;
carrying out one or more of selecting raw tea leaves, specifying the conditions of extraction, filtration, or formulation, or specifying the formulating materials and their ratios, where the strictinin content to be at or below the predetermined level as an indicator; and
carrying out a heat-sterilization process for the tea extract or formulation containing the strictinin at or below the predetermined level. - A manufacturing process for preparing a tea beverage of claim 1,
characterized in
determining the strictinin content in a tea extract or formulation before treating it with heat-sterilization, where the strictinin content to be at or below the predetermined level by treating the above-obtained tea extract or formulation as an indicator; and
carrying out the heat-sterilization process for the tea extract or formulation containing the strictinin at or below the predetermined level. - The manufacturing process for preparing a tea beverage of claims 2-4, in the case of light-fermented tea, wherein the determined strictinin content in a tea extract or formulation to be at about 14 ppm or less as an indicator.
- The manufacturing process for preparing a tea beverage of claims 2-4, in the case of light-fermented tea, wherein the tea solid portion in the tea extract or formulation to be about 0.5-1.1% or less as an indicator.
- The manufacturing process for preparing a tea beverage of claims 2-4, in the case of non-fermented tea, wherein the determined strictinin content in a tea extract or formulation to be at about 6 ppm or less as an indicator.
- The manufacturing process for preparing a tea beverage of claims 2-4, in the case of non-fermented tea, wherein the tea solid portion in the tea extract or formulation to be about 0.2-0.5% or less as an indicator.
- A manufacturing process for preparing a light-fermented tea beverage comprising the following steps:an extraction process extracting raw tea leaves,a filtration process filtrating the extract,a formulation process adjusting the concentration of extract and pH, anda sterilization process sterilizing the formulation,
the determined strictinin content in the tea extract or formulation of before-heat-sterilization to be at about 14 ppm or less, or the tea solid portion in the tea extract or formulation to be about 0.5-1.1% or less. - A manufacturing process for preparing a non-fermented tea beverage comprising the following steps:an extraction process extracting raw tea leaves,a filtration process filtrating the extract,a formulation process adjusting the concentration of extract and pH, anda sterilization process sterilizing the formulation,
the determined strictinin content in the tea extract or formulation of before-heat-sterilization to be at about 6 ppm or less, or the tea solid portion in the tea extract or formulation to be about 0.2-0.5% or less.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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JP2002043974A JP3626462B2 (en) | 2002-02-20 | 2002-02-20 | Method for producing tea beverage |
JP2002043974 | 2002-02-20 |
Publications (2)
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EP1338207A1 true EP1338207A1 (en) | 2003-08-27 |
EP1338207B1 EP1338207B1 (en) | 2008-04-09 |
Family
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EP03003706A Expired - Lifetime EP1338207B1 (en) | 2002-02-20 | 2003-02-19 | Manufacturing process of tea beverages |
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US (1) | US6797305B2 (en) |
EP (1) | EP1338207B1 (en) |
JP (1) | JP3626462B2 (en) |
DE (1) | DE60320162T2 (en) |
Cited By (1)
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EA020611B1 (en) * | 2008-10-02 | 2014-12-30 | Унилевер Н.В. | Process for manufacturing tea product, tea product and health-improving composition |
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US20130202769A1 (en) * | 2010-10-12 | 2013-08-08 | Steven Peter Colliver | Process for manufacturing green tea |
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH03280832A (en) * | 1990-03-29 | 1991-12-11 | Nitto Denko Corp | Production of tea drink |
JPH04311348A (en) * | 1991-04-11 | 1992-11-04 | Itouen:Kk | Preparation of green tea drink |
US5258188A (en) * | 1989-04-06 | 1993-11-02 | Thomas J. Lipton Co., Division Of Conopco, Inc. | Process of preparing a tea product |
JPH1156241A (en) * | 1997-08-08 | 1999-03-02 | Asahi Inriyou Kk | Production of tea drink |
US6268099B1 (en) * | 1996-05-28 | 2001-07-31 | Fuji Xerox Co., Ltd. | Toners, process for the preparation thereof, developers and method of forming images |
Family Cites Families (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1518794A (en) * | 1974-09-17 | 1978-07-26 | Dej Internationale Research Co | Tea extract |
JPS6336745A (en) | 1986-07-31 | 1988-02-17 | Potsuka Corp:Kk | Treatment of extracted tea |
JPH01156241A (en) | 1987-12-10 | 1989-06-19 | Matsushita Electric Ind Co Ltd | Paper feeder |
JPH0445744A (en) | 1990-06-13 | 1992-02-14 | Itouen:Kk | Production of clear green tea drink |
JP2613163B2 (en) | 1993-03-18 | 1997-05-21 | 株式会社ポッカコーポレーション | Tea beverage and method for producing the same |
JPH06311847A (en) | 1993-04-28 | 1994-11-08 | J A Foods Ooita:Kk | Production of clear green tea beverage |
JPH06336745A (en) | 1993-05-26 | 1994-12-06 | Takamura Kenzai Kogyo Kk | Leakage preventing construction between precast side frame and precast bottom plate of water storage tank |
JPH08228684A (en) | 1995-03-01 | 1996-09-10 | Yakult Honsha Co Ltd | Production of green tea beverage |
JP3152416B2 (en) | 1996-12-12 | 2001-04-03 | 株式会社 伊藤園 | Tea production method |
JP3096035B1 (en) | 1999-08-05 | 2000-10-10 | 三井農林株式会社 | Method for producing green tea beverage and green tea beverage produced by the method |
JP3694733B2 (en) * | 2000-06-29 | 2005-09-14 | 独立行政法人農業・生物系特定産業技術研究機構 | Antiallergic agent |
-
2002
- 2002-02-20 JP JP2002043974A patent/JP3626462B2/en not_active Expired - Lifetime
-
2003
- 2003-02-19 EP EP03003706A patent/EP1338207B1/en not_active Expired - Lifetime
- 2003-02-19 DE DE60320162T patent/DE60320162T2/en not_active Expired - Lifetime
- 2003-02-20 US US10/368,641 patent/US6797305B2/en not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5258188A (en) * | 1989-04-06 | 1993-11-02 | Thomas J. Lipton Co., Division Of Conopco, Inc. | Process of preparing a tea product |
JPH03280832A (en) * | 1990-03-29 | 1991-12-11 | Nitto Denko Corp | Production of tea drink |
JPH04311348A (en) * | 1991-04-11 | 1992-11-04 | Itouen:Kk | Preparation of green tea drink |
US6268099B1 (en) * | 1996-05-28 | 2001-07-31 | Fuji Xerox Co., Ltd. | Toners, process for the preparation thereof, developers and method of forming images |
JPH1156241A (en) * | 1997-08-08 | 1999-03-02 | Asahi Inriyou Kk | Production of tea drink |
Non-Patent Citations (5)
Title |
---|
CLIFFORD M N ET AL: "Ellagitannins - nature, occurrence and dietary burden.", JOURNAL OF THE SCIENCE OF FOOD AND AGRICULTURE 80 (7) 1118-1125 2000 SCH. OF BIOL. SCI., UNIV. OF SURREY, GUILDFORD GU2 5XH, UK. E-MAIL M.CLIFFORD(A)SURREY. AC.UK, XP002242745 * |
NONAKA G I ET AL: "Hydrolysable tannins and proanthocyanidins from green tea.", PHYTOCHEMISTRY 1984 FAC. OF PHARMACEUTICAL SCI., KYUSHU UNIV. 62, MAIDASHI HIGASHI-KU, FUKUOKA 812, JAPAN, vol. 23, no. 8, pages 1753 - 1755, XP001152548 * |
PATENT ABSTRACTS OF JAPAN vol. 016, no. 106 (C - 0919) 16 March 1992 (1992-03-16) * |
PATENT ABSTRACTS OF JAPAN vol. 017, no. 135 (C - 1037) 19 March 1993 (1993-03-19) * |
PATENT ABSTRACTS OF JAPAN vol. 1999, no. 08 30 June 1999 (1999-06-30) * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN105248707A (en) * | 2015-11-20 | 2016-01-20 | 西双版纳慧莹贸易有限公司 | Processing method of scented Puer tea |
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JP2003235452A (en) | 2003-08-26 |
JP3626462B2 (en) | 2005-03-09 |
EP1338207B1 (en) | 2008-04-09 |
DE60320162D1 (en) | 2008-05-21 |
US6797305B2 (en) | 2004-09-28 |
DE60320162T2 (en) | 2009-05-28 |
US20030185950A1 (en) | 2003-10-02 |
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